一个新的有机催化概念,用于非对称的化的α-化
Lorenzo Caruana1, Florian Kniep, Tore Kiilerich Johansen
1Center for Catalysis, Department of Chemistry, Aarhus University , DK-8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|November 5, 2014
概括
这项研究引入了一种使用有机催化剂合成复杂化物的新方法. 该过程有效地产生了具有多个立体中心的分子,为有价值的化学化合物提供了直接的途径.
科学领域:
- 有机化学 有机化学
- 不对称的催化剂.
- 合成方法论 合成方法论
背景情况:
- 有机催化不对称的α-化对于合成性分子至关重要.
- 胺催化为碳-碳键形成提供了一个强大的策略.
- 在有机合成中,p-昆甲基是多功能电友.
研究的目的:
- 开发一种新的有机催化方法,用于化物α-化.
- 为了实现不对称的1,6-结合的胺添加到p-金甲基化物中.
- 用两个连续的立体中心合成α-二甲基替代化物.
主要方法:
- 利用一种新开发的性二次氨基催化剂.
- 从化物中获得的胺被使用.
- 通过1,6-结合添加与p-氨基甲基发生反应的酶胺.
主要成果:
- 成功合成了α-diarylmethine替代的化物.
- 在两个连续立体中心的形成中实现了良好的 diastereocontrol.
- 在催化过程中表现出极好的反选择性.
结论:
- 开发的有机催化系统提供了一条简单而有效的途径,以获得有价值的性化物.
- 新的性二次氨基催化剂对于不对称的α-基化是有效的.
- 这种方法推进了具有高立体化学控制的复杂分子的合成.
相关概念视频
α-Alkylation of Ketones via Enolate Ions
2.2K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
2.2K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
3.1K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
3.1K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
19.7K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
19.7K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
2.6K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
2.6K
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
8.0K
Similar to water, alcohols can add to the carbonyl carbon of the aldehydes and ketones. The addition of one molecule of alcohol to the carbonyl compound forms the hemiacetal or half acetal. As depicted below, in a hemiacetal, the carbon is directly linked to an OH and OR group.
8.0K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
6.7K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
6.7K


